Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

• derivative 11 was obtained by cyclization with 3 equivalents of potassium O-ethyl xanthate. It was then treated with a methanolic ammonia solution to give triol compound 12. The protection of the cis-2,3-vicinal hydroxy groups of 12 with an isopropylidene, followed by benzoylation, gave compound 13. Using 2

• transesterification to give the hemithioacetal 39, which cyclized to the oxathiolane 40 in situ with minor isomerization. The reduction of the ester group with LiAlH4, followed by benzoylation using benzoyl chloride and pyridine gave 1,3-oxathiolane derivative 41. Kraus and Attardo [48] developed new strategies for

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98

• mixture of E/Z isomers. Further, double bond cleavage of nucleoside 120 followed by benzoylation produced the benzoic acid ester of the hemiacetal analogue 121 which was finally converted into double-headed nucleoside 122 via Vorbrüggen coupling reaction followed by deprotection using methanolic ammonia

Beyond ribose and phosphate: Selected nucleic acid modifications for structure–function investigations and therapeutic applications

• Christopher Liczner,
• Kieran Duke,
• Gabrielle Juneau,
• Martin Egli and
• Christopher J. Wilds

Beilstein J. Org. Chem. 2021, 17, 908–931, doi:10.3762/bjoc.17.76

• iodide and silver oxide. The protected adenine base was regenerated by treatment with ammonia followed by benzoylation. Once the methyl group was incorporated into these ribonucleosides, the TIPDS group was selectively removed by tetrabutylammonium fluoride (TBAF) or hydrochloric acid treatment, followed

Synthesis of Streptococcus pneumoniae serotype 9V oligosaccharide antigens

• Sharavathi G. Parameswarappa,
• Claney L. Pereira and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2020, 16, 1693–1699, doi:10.3762/bjoc.16.140

• was modified into compound 6 via benzylidene ring opening followed by benzoylation of the free C-4 secondary hydroxy group in 27. The disaccharide imidate 29 was synthesized from 6 by anomeric desilylation to afford 28 that was converted to the corresponding imidate in an excellent yield. The final [2

SnCl₄-catalyzed solvent-free acetolysis of 2,7-anhydrosialic acid derivatives

• Kesatebrhan Haile Asressu and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2019, 15, 2990–2999, doi:10.3762/bjoc.15.295

• -benzoylation of 2 with benzoyl chloride in pyridine produced compound 9 in a moderate yield of 57% (Scheme 2) [34]. Wong and co-workers reported the major effects of the carboxy group on the anomeric reactivity of sialic acid compared with the side chain protecting groups. Hence, we converted 2 into O-acetyl

Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study

• Enrique A. Del Vigo,
• Carlos A. Stortz and
• Carla Marino

Beilstein J. Org. Chem. 2019, 15, 2982–2989, doi:10.3762/bjoc.15.294

• the yields. Methyl galactopyranosides 7 and 8 were synthesized from per-O-benzoyl-α-ᴅ-Galp (6), prepared by benzoylation of galactose in pyridine [16] at low temperature (0 ºC) in order to avoid the formation of furanosic forms, which are usually generated from ᴅ-Gal [17]. The β-anomer 7 was obtained

• and mixed acetals [21][22]. Either by benzoylation or benzylation of 9α or 9β and subsequent deisopropylidenation, glycosyl acceptors 1α/β and 2α/β were efficiently obtained (Scheme 1). Compounds 1α and 1β were previously prepared, but in lower yield [23][24], and compound 2α was obtained as a

Chemical synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from Escherichia coli O132 in the form of its 2-aminoethyl glycoside

• Debasish Pal and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2019, 15, 2563–2568, doi:10.3762/bjoc.15.249

• subjected to Zemplén de-O-benzoylation using NaOMe in MeOH to give compound 13 in 93% yield. Further, per-O-benzylation using BnBr in the presence of NaH [22] afforded the galactofuranosyl donor 14 in 89% yield. Glycosylation of the donor 14 with known rhamnose acceptor 15 [23] through activation of the

A metal-free approach for the synthesis of amides/esters with pyridinium salts of phenacyl bromides via oxidative C–C bond cleavage

• Kesari Lakshmi Manasa,
• Yellaiah Tangella,
• Namballa Hari Krishna and
• Mallika Alvala

Beilstein J. Org. Chem. 2019, 15, 1864–1871, doi:10.3762/bjoc.15.182

• 10.3762/bjoc.15.182 Abstract An efficient, simple, and metal-free synthetic approach for the N- and O-benzoylation of various amines/benzyl alcohols with pyridinium salts of phenacyl bromides is demonstrated to generate the corresponding amides and esters. This protocol facilitates the oxidative cleavage

• functional group tolerance, broad substrate scope and operational simplicity are the prominent advantages of the current protocol. Keywords: amidation; benzoylation; benzylamines; pyridinium salt of phenacyl bromides; Introduction Amidation and esterification are fundamental transformations in synthetic

• work-up procedures and the requirement of stoichiometric amounts of coupling reagents. On the other hand, benzoylation reactions are usually performed with benzoyl chloride or benzoic anhydride which results in the formation of a substantial amount of undesired chemical waste. Moreover, these benzoic

Anomeric sugar boronic acid analogues as potential agents for boron neutron capture therapy

• Daniela Imperio,
• Erika Del Grosso,
• Silvia Fallarini,
• Grazia Lombardi and
• Luigi Panza

Beilstein J. Org. Chem. 2019, 15, 1355–1359, doi:10.3762/bjoc.15.135

• protected sugar precursors (Figure 3). The synthesis of the first analogue 8, shown in Scheme 1, started from known compound 1, that is easily obtained from 2,3,5-tri-O-benzyl-ᴅ-arabinose according to a literature procedure [15]. Benzoylation of the free hydroxy group of 1, followed by removal of the silyl

6’-Fluoro[4.3.0]bicyclo nucleic acid: synthesis, biophysical properties and molecular dynamics simulations

• Sibylle Frei,
• Andrei Istrate and
• Christian J. Leumann

Beilstein J. Org. Chem. 2018, 14, 3088–3097, doi:10.3762/bjoc.14.288

• of the nucleobase was partially removed. As a consequence an additional benzoylation step was needed to obtain the allylic alcohol 14 in high yields. Verification of the configuration at C(5’) was again accomplished by 1H,1H-ROESY experiments (Supporting Information File 1). Tritylation of the

Practical tetrafluoroethylene fragment installation through a coupling reaction of (1,1,2,2-tetrafluorobut-3-en-1-yl)zinc bromide with various electrophiles

• Ken Tamamoto,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2018, 14, 2375–2383, doi:10.3762/bjoc.14.213

• °C for 20 h enabled the formation of the corresponding cross-coupling reaction product 6a in 67% yield (Table 3, entry 1). Optimization of the Cu(I) catalyst for the benzoylation reaction (Table 3, entries 2–4) revealed that Cu2O was the most efficient for producing 6a (81% by NMR, Table 3, entry 4

Anomeric modification of carbohydrates using the Mitsunobu reaction

• Julia Hain,
• Patrick Rollin,
• Werner Klaffke and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2018, 14, 1619–1636, doi:10.3762/bjoc.14.138

• results outlined in Scheme 16 are consistent with early findings of Guthrie et al. exploring the Mitsunobu benzoylation of 4,6-O-benzylidene-D-allal [73]. Reactions with alcohols to yield alkyl glycosides In contrast to aryl ethers, the formation of alkyl ethers is not observed under Mitsunobu conditions

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• stereoselective trans iodo-benzoylation of glycals using a combination of IBX and molecular iodine, that is considered as a source of I+ formed from the in situ generated hypoiodite species [30]. The controlled oxidation of various N-(alkyl)- and N-(aryl)pyrroles with Dess–Martin periodinane also leads to

Mechanochemistry of nucleosides, nucleotides and related materials

• Olga Eguaogie,
• Joseph S. Vyle,
• Patrick F. Conlon,
• Manuela A. Gîlea and
• Yipei Liang

Beilstein J. Org. Chem. 2018, 14, 955–970, doi:10.3762/bjoc.14.81

• observed within one to three hours and only in the case of adenosine was any (minor) side-product formation found. In all cases, facile purification using a scrubber column enabled pure 2′,3′,5′-tri-O-TBDMS-protected nucleosides to be isolated in 87–99% yields. In situ benzoylation of the persilylated

Development of a method for the synthesis of 2,4,5-trisubstituted oxazoles composed of carboxylic acid, amino acid, and boronic acid

• Kohei Yamada,
• Naoto Kamimura and
• Munetaka Kunishima

Beilstein J. Org. Chem. 2017, 13, 1478–1485, doi:10.3762/bjoc.13.146

• carboxylic acid 1 and amino acid 2 under conditions improved from [23] (Table 1). A one-pot sequence involving formation of an activated ester from benzoic acid (1a) with DMT-MM, N-benzoylation of alanine (2a), cyclodehydration, and introduction of the triazinyl group was conducted in 1,4-dioxane/H2O to give

Synthesis and in vitro cytotoxicity of acetylated 3-fluoro, 4-fluoro and 3,4-difluoro analogs of D-glucosamine and D-galactosamine

• Štěpán Horník,
• Lucie Červenková Šťastná,
• Petra Cuřínová,
• Jan Sýkora,
• Kateřina Káňová,
• Roman Hrstka,
• Ivana Císařová,
• Martin Dračínský and
• Jindřich Karban

Beilstein J. Org. Chem. 2016, 12, 750–759, doi:10.3762/bjoc.12.75

• :2,3-dianhydro-4-O-benzyl-β-D-mannopyranose (10, one of the Černý epoxides available from D-glucal [31][32][33] or levoglucosan [34]). Regioselective azidolysis [21][35][36] of 10 yielded 2-azido alcohol 11 which was converted to 12 by benzoylation at O-3 and debenzylation at O-4. To prevent azide

Synthesis of the pentasaccharide repeating unit of the O-antigen of E. coli O117:K98:H4

• Pintu Kumar Mandal

Beilstein J. Org. Chem. 2014, 10, 2724–2728, doi:10.3762/bjoc.10.287

• acid on silica (HClO4/SiO2) [28][29] afforded 3-azidopropyl (2,3-di-O-benzyl-β-D-glucopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-galactopyranoside (9) in 85% yield. Selective 6-O-benzoylation of compound 9 was accomplished with benzoyl cyanide [30] to furnish disaccharide acceptor 10 in 80% yield

Visible light photoredox-catalyzed deoxygenation of alcohols

• Daniel Rackl,
• Viktor Kais,
• Peter Kreitmeier and
• Oliver Reiser

Beilstein J. Org. Chem. 2014, 10, 2157–2165, doi:10.3762/bjoc.10.223

• acids (Supporting Information File 1) it was found that 6e could be selectively prepared by copper(II) chloride-catalyzed benzoylation of diol 8 with anhydride 9, which in turn can be generated from its acid 5 by treatment with acetic anhydride (Scheme 6). Since acetic anhydride is technically being

Synthesis of phosphoramidites of isoGNA, an isomer of glycerol nucleic acid

• Keunsoo Kim,
• Venkateshwarlu Punna,
• Phaneendrasai Karri and
• Ramanarayanan Krishnamurthy

Beilstein J. Org. Chem. 2014, 10, 2131–2138, doi:10.3762/bjoc.10.220

• stable under these conditions (Table 1, entry 1). 50% of TFA in CH2Cl2 completely removed both Boc groups on adenine at either 4 °C or rt to afford the desired 33 in 87% yield. The trityl group was reintroduced on 33 under standard conditions to give 34, and subsequent benzoylation afforded 26 in overall

• di-Boc-adenine. An attempt to remove both Boc and silyl groups simultaneously. The synthesis of 26 via tritylation and benzoylation. Result of Boc deprotection of 29 with TFA. Supporting Information Supporting Information File 409: Experimental procedures. Supporting Information File 410: 1H, 13C

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

Concise total synthesis of two marine natural nucleosides: trachycladines A and B

• Haixin Ding,
• Wei Li,
• Zhizhong Ruan,
• Ruchun Yang,
• Zhijie Mao,
• Qiang Xiao and
• Jun Wu

Beilstein J. Org. Chem. 2014, 10, 1681–1685, doi:10.3762/bjoc.10.176

• environment of 2-OH the benzoylation with benzoyl chloride required an extended reaction time (48 h) and 2 equiv DMAP as base and catalyst. At last, the 1-O-methyl group was transformed to 1-O-acetate glycosylation acceptor 4 as an anomeric mixture (α:β = 2:3) in 84% yield. Therefore, the key intermediate 4

Stereoselective synthesis of carbocyclic analogues of the nucleoside Q precursor (PreQ₀)

• Sabin Llona-Minguez and
• Simon P. Mackay

Beilstein J. Org. Chem. 2014, 10, 1333–1338, doi:10.3762/bjoc.10.135

• following syn-dihydroxylation. Using the Upjohn conditions previously described we obtained the desired triol 18 in good yield and excellent diastereoselectivity (>99% by 1H NMR after column chromatography) [30]. Tri-benzoate 19 was subsequently obtained in good yield using the standard benzoylation

Olefin cross metathesis based de novo synthesis of a partially protected L-amicetose and a fully protected L-cinerulose derivative

• Bernd Schmidt and
• Sylvia Hauke

Beilstein J. Org. Chem. 2014, 10, 1023–1031, doi:10.3762/bjoc.10.102

• benzoylation in pyridine resulted exclusively in the formation of furan 10 (Table 2, entry 1). We reasoned that pyridine initiates an E/Z-isomerization of the enal through nucleophilic attack at the β-position, followed by lactol formation, benzoylation of the lactol and finally elimination of benzoic acid

• better results were obtained with two different phosphine free catalysts comprising a hemilabile alkoxy substituted benzylidene ligand, even at only moderately elevated temperatures. The acrolein cross metathesis product can be converted into the 4-benzoate of L-amicetose via benzoylation, Pd-catalyzed